[PtMe₂(di-2-pyridyl ketone)] | 869378-45-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [PtMe₂(di-2-pyridyl ketone)]
• 英文别名: Carbanide;dipyridin-2-ylmethanone;platinum(2+)
• CAS: 869378-45-0
• 化学式: C₁₃H₁₄N₂OPt
• 分子量: 409.347
• InChiKey: LDOFFDZERCZDBP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [PtMe₂(di-2-pyridyl ketone)] 以 further solvent(s) 、 not given 为溶剂， 生成 (2,2-联吡啶)二氯铂(II)
  参考文献：
  名称：

  Activation of Anisole by Organoplatinum(II) Complexes: Evidence for Rate-Determining C–H Activation

  摘要：

  A study of the basis of selectivity of C-H bond activation of anisole by electrophilic methylplatinum(II) complexes is reported. Anisole reacts with [PtXMe(NN)] in trifluoroethanol solvent to give methane and [PtXAr(NN)], Ar = 2-, 3-, and 4-anisyl, in 90:8:2 ratio when X = HOB(C6F5)(3) and NN = (2-C5H4N)(2)CO (DPK) but not when NN = 2,2'-bipyridine. Similar results are obtained when X = triflate or when NN = (2-C5H4N)(2)NH. Competition between reaction of anisole and anisole-d(8) with [PtXMe(NN)], X = HOB(C6F5)(3) and NN = DPK, in trifluoroethanol gave an isotope effect k(H)/k(D) = 3.6. Several 4-anisyl complexes, [PtClAr(NN)], [PtAr2(NN)], and [PtMeAr(NN)], NN = DPK, DPA, or bipy, were prepared and reacted with HX [X = Cl, OTf, or HOB(C6F5)(3)]. Reaction of [PtMeAr(NN)], NN = DPK or bipy, with HX gave a detectable hydride [PtXHMeAr(NN)] when X = Cl, followed by loss of methane to give [PtClAr(NN)], but only [Pt(OTf)Ar(NN)] was detected when X = OTf. Reaction with more HOTf gave anisole and [PtX2(NN)], X = OTf, and no isomerization of the 4-anisyl group to the more favored 2-anisyl group was observed at any stage. The similar reaction of [PtMeAr(NN)] and HOTf in CD3OD/CD2Cl2 gave CHnD4-n (n = 0-4) and mostly 4-MeOC6H4D. It is argued that the anisole C-H bond cleavage step in anisole activation, or the anisyl-H bond forming step in protonolysis, is responsible for the observed selectivity in these reactions.

  DOI：

  10.1021/om200922a
• 作为产物：
  描述：

  2-二吡啶基酮 、 bis[dimethyl(μ-dimethylsulfide)platinum(II)] 以 二氯甲烷 为溶剂， 以90%的产率得到[PtMe₂(di-2-pyridyl ketone)]
  参考文献：
  名称：

  二甲基（二吡啶基酮）铂（II）的氧化加成化学

  摘要：

  二甲基铂 (II) 络合物 [PtMe2(DPK)] (DPK = di-2-pyridyl ketone) 容易氧化加成得到铂 (IV) 络合物。例如，[PtMe2(DPK)]与MeI反应得到[PtIM...

  DOI：

  10.1139/v05-028

文献信息

• Activation of C−H Bonds of Arenes:  Selectivity and Reactivity in Bis(pyridyl) Platinum(II) Complexes
  作者：Fenbao Zhang、Christopher W. Kirby、Douglas W. Hairsine、Michael C. Jennings、Richard J. Puddephatt

  DOI：10.1021/ja055436z

  日期：2005.10.1

  The reaction of [PtMe2(NN)] and B(C6F5)3/H2O in CF3CH2OH with arenes Ar-H gives [PtArHOB(C6F5)3}(LL)] if the bis(pyridyl) ligand NN forms a six-membered, but not five-membered, chelate ring; methyl-substituted arenes give selectivity for metalation of meta > para > ortho, but methoxy-substituted arenes give ortho > meta, para.

  [PtMe2(NN)] 和 B(C6F5)3/H2O 在 CF3C H 中与芳烃 Ar-H 的反应得到 [PtArHOB( )3}(LL)] 如果双（吡啶基）配体 NN 形成六-成员，但不是五成员，螯合环；甲基取代的芳烃对间位 > 对位 > 邻位的金属化具有选择性，但甲氧基取代的芳烃可以使邻位 > 间位，对位。
• Hydridodimethylplatinum(IV) Complexes with Bis(pyridine) Ligands:  Effect of Chelate Ring Size on Reactivity
  作者：Fenbao Zhang、Ernest M. Prokopchuk、Michael E. Broczkowski、Michael C. Jennings、Richard J. Puddephatt

  DOI：10.1021/om050982m

  日期：2006.3.1

  dimethylplatinum(II) complexes [PtMe2(LL)] has been studied, by comparing complexes with the ligands LL = di-2-pyridylamine (DPA) or di-2-pyridyl ketone (DPK), which form a six-membered chelate ring, to compounds with 2,2‘-bipyridyl derivatives, which form a five-membered chelate ring. The complex [PtMe2(DPA)] undergoes easy oxidative addition of methyl iodide to give the corresponding platinum(IV) complex [PtIMe3(DPA)]

  通过与配体LL =二-2-吡啶胺（DPA）或配体进行比较，研究了改变二吡啶基配体LL的咬合角对二甲基铂（II）配合物[PtMe 2（LL）]的反应性的影响。形成六元螯合环的二-2-吡啶基酮（DPK）与具有五元螯合环的2,2'-联吡啶基衍生物的化合物。配合物[PtMe 2（DPA）]易于氧化碘甲烷，得到相应的铂（IV）配合物[PtIMe 3（DPA）]。[PtMe 2（DPA）]和[PtMe 2（DPK）]均在低温下被酸HX质子化，得到氢化二甲基铂（IV）络合物[PtHXMe 2（NN）]和[PtH（S）Me 2（NN）] X（S =溶剂），可以两种异构形式存在，H转化为X或N。配合物[PtHClMe 2（DPK）]的结构由晶体学确定。在含有过量CD 3 OD的溶液中，低温下会发生广泛的氢/氘交换成甲基铂基团和甲烷产物，这表明氢化甲基铂（IV）和（甲烷）铂（II）配合物之间的交换非常容易可逆。与NN
• Organoplatinum(IV) complexes with functional alkyl groups and their use in supramolecular chemistry
  作者：Richard H.W. Au、Lisa J. Findlay-Shirras、Neil M. Woody、Michael C. Jennings、Richard J. Puddephatt

  DOI：10.1139/v09-031

  日期：2009.7

  The oxidative addition of alkyl bromides RCH₂Br (R = C₅H₄N, C₆H₄CN, CH₂C₆H₄CO₂H, or CH₂C₆H₄CH₂CO₂H) to dimethylplatinum(II) complexes [PtMe₂(LL)] (LL = diimine ligand) gives the corresponding organoplatinum(IV) complexes [PtBrMe₂(CH₂R)(LL)] containing functionality in the alkyl group RCH₂. The pyridyl derivatives can be protonated, while abstraction of the bromide ligand from [PtBrMe₂(CH₂R)(LL)] can form cationic complexes, which can react with water or form oligomers by self-assembly.

  将烷基溴 RCH2Br（R = C5H4N、C6H4CN、CH2C6H4CO2H 或 CH2C6H4CH2CO2H）氧化添加到二甲基铂（II）络合物 [PtMe2(LL)]（LL = 二亚胺配体）中，可得到相应的有机铂（IV）络合物 [PtBrMe2(CH2R)(LL)]，其中的烷基 RCH2 具有官能团。吡啶衍生物可以质子化，而从[PtBrMe2(CH2R)(LL)]中抽取溴配体可以形成阳离子配合物，这些配合物可以与水反应或通过自组装形成低聚物。
• Oxidation of dimethylplatinum(ii) complexes with a peroxyacid
  作者：Kyle R. Pellarin、Matthew S. McCready、Richard J. Puddephatt

  DOI：10.1039/c3dt50585e

  日期：——

  [Pt(OH)(OH2⋯O2C-3-C6H4Cl)Me2(NN)], NN = bipy, 3a; dpa, 3b; bebipy, 3d, or [Pt(OH)2Me2(dpkOH)]3[Pt(OH)(OH2)Me2(dpkOH)][H(O2C-3-C6H4Cl)2]·2MeOH, 43·5·2MeOH. The reactions are proposed to occur by a polar oxidative addition mechanism, followed in most cases by the coordination of water. Complex 3a crystallises as a supramolecular polymer, the compound 43·5·2MeOH crystallises as a supramolecular sheet structure

  络合物[PTMe 2（NN）]，NN =2,2'-联吡啶 = 比比，1a ; NN =二-2-吡啶胺= dpa，1b ; NN =二-2-吡啶基酮= dpk，1c，NN =4,4'-双（乙氧羰基）-2,2'-联吡啶，bebipy，与 间氯过氧苯甲酸得到铂（IV）配合物[PT（OH）（O 2 C-3-C 6 H 4 Cl）Me 2（NN）]，NN =比比，2或[PT（OH）（OH 2 ⋯O 2 C-3-C 6 H 4 Cl）Me 2（NN）]，NN =比比，3a ; dpa，3b ; bebipy，3D，或[PT（OH）2我2（dpkOH）] 3 [PT（OH）（OH 2）Me 2（dpkOH）] [H（O 2 C-3-C 6 H ^ 4 Cl）的2 ] ·2MeOH，4 3 · 5 ·2MeOH。该反应被认为是通过极性氧化加成机理发生的，然后在大多数情况下是通过水。配合物3a结晶为超分子聚合物，化合物4
• Oxidative Addition of Phthaloyl Peroxide to Dimethylplatinum(II) Complexes
  作者：Kyle R. Pellarin、Matthew S. McCready、Thomas I. Sutherland、Richard J. Puddephatt

  DOI：10.1021/om3009074

  日期：2012.12.10

  the case with NN = dpa, no phthalate chelate complex is formed. These complexes are easily hydrolyzed, and the complexes cis-[PtMe2(OH)κ1-O-O2CC6H4-2-CO2H}(bipy)] and trans-[PtMe2κ1-O-O2CC6H4-2-CO2H}(dpkOH)] have been structurally characterized. It is argued that the oxidative addition of phthaloyl peroxide occurs by a polar mechanism and that the hydrolysis is easy because there is no special stability

  配合物[PTMe 2（NN）]，其中NN = 2,2'-联吡啶（bipy），4,4'-二叔丁基-2,2'-联吡啶（bu 2 bipy），二-2-吡啶胺（DPA），或二-2-吡啶基酮（DPK），邻苯二甲与过氧化，得到螯合配合物的混合物[PTME容易反应2 κ 2 - ø，ö '-1,2-（O 2 C）2 ç 6 ħ 4 }（NN）]，其在结构上表征当NN = BU 2联吡啶，和低聚物或聚合物[PTME 2 μ-κ 2 - ø，ö '-1,2-（O 2 C）2C 6 H 4 }（NN）] n。在NN = dpa的情况下，不会形成邻苯二甲酸盐螯合物。这些复合物被容易水解，复合物的顺式- [PTME 2（OH）κ 1 - ö -O 2 CC 6 H ^ 4 -2-CO 2 H}（联吡啶）〕和反式- [PTME 2 κ 1 - O -O 2 CC 6 H 4 -2-CO 2H}（dpkOH）